CN102703887A - Nickel-copper alloy liquid for chemical plating and electroplating and method for preparing nickel-copper alloy noncrystalline-based composite coating - Google Patents
Nickel-copper alloy liquid for chemical plating and electroplating and method for preparing nickel-copper alloy noncrystalline-based composite coating Download PDFInfo
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- CN102703887A CN102703887A CN2012101776241A CN201210177624A CN102703887A CN 102703887 A CN102703887 A CN 102703887A CN 2012101776241 A CN2012101776241 A CN 2012101776241A CN 201210177624 A CN201210177624 A CN 201210177624A CN 102703887 A CN102703887 A CN 102703887A
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- electroless plating
- nickel
- copper alloy
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- 238000007747 plating Methods 0.000 title claims abstract description 71
- 238000000576 coating method Methods 0.000 title claims abstract description 56
- 239000011248 coating agent Substances 0.000 title claims abstract description 55
- 239000007788 liquid Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title abstract description 20
- 238000009713 electroplating Methods 0.000 title abstract description 8
- 239000000126 substance Substances 0.000 title abstract description 7
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 title abstract 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 51
- 230000008021 deposition Effects 0.000 claims abstract description 20
- 150000002815 nickel Chemical class 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000008139 complexing agent Substances 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 41
- 238000000151 deposition Methods 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 238000007772 electroless plating Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000005253 cladding Methods 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 230000002829 reductive effect Effects 0.000 claims description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 claims description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 229960003280 cupric chloride Drugs 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- DQZXOIPVJBKPAK-UHFFFAOYSA-L potassium;sodium;phosphono phosphate Chemical compound [Na+].[K+].OP(O)(=O)OP([O-])([O-])=O DQZXOIPVJBKPAK-UHFFFAOYSA-L 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 5
- 229940038773 trisodium citrate Drugs 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 2
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 claims description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 2
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 150000001879 copper Chemical class 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 12
- 238000012545 processing Methods 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 8
- 239000004141 Sodium laurylsulphate Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 8
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000005137 deposition process Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002707 nanocrystalline material Substances 0.000 description 4
- 229910000085 borane Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000012669 liquid formulation Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 241001156002 Anthonomus pomorum Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 atoms metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
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- 239000007769 metal material Substances 0.000 description 1
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Abstract
The invention provides nickel-copper alloy liquid for chemical plating and electroplating. The nickel-copper alloy liquid for the chemical plating and the electroplating comprises 1-10g/L of copper salt, 20-60g/L of nickel salt, 10-20g/L of complexing agent and 1-10g/L of reducing agent by taking deionized water as a solvent. By using the nickel-copper alloy liquid, a nickel-copper alloy composite coating is prepared on the surface of a metal base by adopting a method of chemical plating and electroplating synergetic deposition. The coating not only is of a nanocrystalline structure but also is of a noncrystalline structure, and moreover, nanocrystallines are evenly distributed in a noncrystalline continuous phase. The coating is a nickel-copper alloy noncrystalline-based composite coating. The nickel-copper alloy noncrystalline-based composite coating has the properties of the noncrystalline structure and the crystalline structure, thus, the combination property of the coating is obviously improved, such as corrosion resistance, wear resistance, high strength, high hardness and excellent room-temperature ductility, and the application range of a metal matrix is greatly broadened.
Description
Technical field
The present invention relates to the preparation of metal material surface coating, plating, electroless plating technology field; Be specifically related to a kind of electroless plating-plating and use corronel liquid; Use this electroless plating-plating to prepare the method for corronel amorphous base composite cladding with corronel liquid, and the corronel composite deposite of the amorphous-nano-crystalline structure for preparing.
Background technology
Plating and electroless plating all have the history in more than 160 year.The history that the industrial application electro-plating method prepares coating has had the quite a while, and it is from General American Transportation company (GATC) beginning of 19th-century fifties that applied chemistry is coated with the coating that is equipped with.The coating of electric plating method preparation is crystalline state or nanocrystalline structure, and the coating of electroless plating preparation can obtain the coating of amorphous to the multiple structure of crystalline state along with the change of reduction dosage.Non-crystalline state and nanocrystalline material have particular structure and a series of good characteristic separately.Amorphous material is because unordered, the short range order characteristics of long-range of its atomic arrangement; On physics, chemistry and mechanical property, show a series of excellent specific properties; Like HS, hardness, erosion resistance, wear resistance etc., however one of gordian technique that bad plasticity is an amorphous material need be solved.Compare with non-crystalline material, nanocrystalline material has the good mechanical performance equally because a large amount of atom is on the crystal boundary, and like high firmness, high-wearing feature etc., nanocrystalline material also has good plasticity and toughness in addition, but its intergranular corrosion is serious.Therefore, how to utilize the mutual supplement with each other's advantages of non-crystal structure and nanocrystalline structure, it is current amorphous, nanocrystalline material hot research fields that preparation has high performance amorphous nano crystal composite material.
Electroplate and electroless plating takes place the earliest to be found when the electric deposition nickel by Brenner and Riddell simultaneously.The research of adopting these two kinds of methods to prepare coating simultaneously at present is fewer.Publication number is the Chinese invention patent of CN101654797A adopts electrochemistry and electroless plating when surface of steel workpiece preplating copper a technology; Obtained very big repercussion; Yet; This method only provides a kind of method of preplating for acid copper-plating, the thickness of coating that obtains is merely several micron dimensions, and its comprehensive mechanical property can not requirement of actual application.Publication number is in the Chinese invention patent of CN1818141A, discloses a kind of plating bath that two kinds of deposition reactions can take place, but these two kinds of depositions are not to take place simultaneously, but the change through reaction conditions makes it under different condition, to take place.Utilize still pettiness of research that electroplating chemical is coated with amorphous nano-crystalline composite deposite fully.
Summary of the invention
Technical purpose of the present invention is to the above-mentioned state of the art, provides two kinds of methods of a kind of electrochemical deposition and electroless plating the collaborative method for preparing ambrose alloy amorphous base composite cladding.This method original position is controlled, and cost is lower, and is simple to operate, and the comprehensive mechanical property of the coating that obtains all improves a lot than crystalline state coating and amorphous deposit.
The present invention realizes that the technical scheme that above-mentioned technical purpose adopts is: corronel liquid is used in a kind of electroless plating-plating, and this alloy liquid is to be solvent with the deionized water, wherein comprises the solute of following percent weight in volume concentration:
Described mantoquita includes but not limited at least a in copper sulfate, cupric pyrophosphate, the cupric chloride;
Described nickel salt includes but not limited at least a in single nickel salt, the nickelous chloride;
Described reductive agent includes but not limited at least a in sodium hypophosphite, amino borane, oxammonium hydrochloride, Peng Qinghuana, formaldehyde, the Hydrazine Hydrate 80;
Described complexing agent includes but not limited at least a in Hydrocerol A, Trisodium Citrate, boric acid, Sodium Tetraborate, potassium pyrophosphate sodium, the trisodium phosphate.
Use electroless plating of the present invention-plating to use corronel liquid, adopt the preparation technology of the collaborative preparation of electroless plating-plating corronel amorphous base composite cladding to comprise the steps:
Step 1, metal substrate surface is carried out oil removing, oxide film dissolving handle;
Step 2, with deionized water mantoquita, nickel salt, complexing agent, reductive agent are prepared electroless plating-plating by weight percentage and use corronel liquid;
The preparation of step 3, corronel amorphous nano-crystalline composite deposite: the metal base after handling in the step 1 is placed the electroless plating-plating of step 2 preparation carry out the collaborative deposition of electroless plating plating with corronel liquid; Its condition is: anode is the pure nickel plate, and cathode current density is 15 ~ 60mA/cm
2, it is 4 ~ 12 that plating bath uses basic soln to regulate pH, and bath temperature is 30 ~ 80 ℃, and depositing time is 1 h ~ 2 hours, and negative electrode moves, stirs plating bath, and circulating filtration is accomplished the preparation of metal base amorphous nano-crystalline composite deposite.
As preferably, described coating deposition rate is 0.2 ~ 1.0um/min.
As preferably, the basic soln in the described step 3 includes but not limited to ammonia soln or sodium hydroxide solution.
In the described step 1, the surface degreasing of metal base preferably adopts following process:
At mass percent concentration 5%～20% NaOH solution; Be to add an amount of sodium lauryl sulphate in 5%～20% the KOH solution perhaps at mass percent concentration; Obtain mixing solutions; Metal base is put into this mixing solutions, be 40 ℃～70 ℃ at cleaning temperature and cleaned 3 minutes～10 minutes down.
Wherein, the concentration of sodium lauryl sulphate in mixing solutions is preferably 0.5g/l～10g/l, further is preferably 2g/l; Cleaning temperature is preferably 60 ℃～70 ℃.
In the described step 1, the surperficial oxide film dissolving of metal base is handled preferred employing mechanical polishing, chemical rightenning is carried out surface film oxide to metal base and removed processing.
Adopt electroless plating of the present invention-plating to use the collaborative corronel amorphous base composite cladding for preparing by at least a composition the in nickel, copper and non-metallic element phosphorus, nitrogen, the carbon; As shown in Figure 1; The structure of composite deposite is brilliant (second phase) structure of amorphous (external phase) clad nano; The nano-crystalline granule size is at 1 ~ 10nm, and nanocrystalline second is evenly distributed in the amorphous external phase mutually.
In sum; The invention provides a kind of electroless plating-plating and use corronel liquid; Adopt the collaborative sedimentary method of electrochemistry plating and electroless plating, prepare the corronel composite deposite in metal substrate surface, this coating has crystalline state (nanocrystalline) and amorphous structure simultaneously; And nanocrystalline second is evenly distributed in the amorphous external phase mutually, is a kind of corronel amorphous base nanometer crystal composite deposite.Compared with prior art, the present invention has following beneficial effect:
(1) not only comprises the ambrose alloy element in the corronel liquid of the present invention; Also comprise reductive agent, therefore, not only power up outside to flow down the electrochemical deposition reaction can take place; Also because there is the existence of reductive agent that the electroless plating reaction can take place in the solution, so be that alloy liquid is used in a kind of electroless plating-plating;
(2) because therefore electrochemical deposition and electroless plating while and difference nucleation and growth can obtain crystalline state nucleation and non-crystalline state nucleation simultaneously, finally obtain the amorphous nano-crystalline composite deposite.And amorphous coating and crystalline state coating have the relative merits of himself separately; Two kinds of structures are created in the same coating simultaneously; Make this coating have the performance of amorphous and two kinds of structures of crystalline state simultaneously; Thereby significantly improve the over-all properties of coating,, expanded the use range of metallic matrix greatly such as corrosion-resistant, wearability, the hard and excellent temperature-room type plasticity of high-strength height;
(3) because the existence of reductive agent, can in plating bath, introduce at least a in non-metallic element phosphorus, carbon, the nitrogen, the atomic radius of non-metallic atom and two kinds of atoms metals of ambrose alloy has bigger difference, and this has also promoted the formation of the amorphous portion of coating.
(4) partly distinguish shared ratio through can control in this composite deposite amorphous portion and crystalline state to what, the adjustment of cathodic current size and bath temperature height of reduction dosage in the plating bath, thereby reach the purpose regulated and control on the composite deposite performance.
Description of drawings
Fig. 1 is the structural representation of the corronel amorphous nano-crystalline composite deposite of the collaborative preparation of electroless plating of the present invention-plating;
Fig. 2 is the TEM photo of the corronel amorphous nano-crystalline composite deposite of the embodiment of the invention 1 preparation.
Embodiment
Below through specific embodiment the present invention is done further explain, it is pointed out that the following stated embodiment is intended to be convenient to understanding of the present invention, and it does not played any qualification effect.
Embodiment 1:
In the present embodiment:
Electroless plating-plating uses the corronel liquid formula to be: solvent is deionized water, cupric phosphate 8g/L, single nickel salt 20g/L, Hydrazine Hydrate 80 1g/L, boric acid 10g/L.
Use the preparation technology of the collaborative preparation of above-mentioned corronel liquid electroless plating-plating corronel amorphous base composite cladding following:
(1) metal base is a soft steel; Metal substrate surface is carried out oil removing, oxide film dissolving pre-treatment; Detailed process is: at mass percent concentration is to add an amount of sodium lauryl sulphate in 10% the NaOH solution; Obtain mixing solutions, the concentration of sodium lauryl sulphate in mixing solutions is 1g/l, and metal base is put into this mixing solutions; Be 50 ℃ at cleaning temperature and cleaned 8 minutes down, adopt mechanical polishing that metal base is carried out surface film oxide then and remove processing;
(2) with deionized water cupric phosphate, single nickel salt, Hydrazine Hydrate 80 and boric acid are configured to electroless plating-plating and use corronel liquid, the wherein wt percentage concentration is: cupric phosphate 8g/L, single nickel salt 20g/L, Hydrazine Hydrate 80 1g/L, boric acid 10g/L;
(3) place the electroless plating-plating of step (2) preparation to carry out electroless plating with corronel liquid the metal base after step (1) processing and electroplate collaborative deposition, its condition is: anode is the pure nickel plate, and cathode current density is 20mA/cm
2, it is 5.5 that plating bath uses ammoniacal liquor to regulate pH, and bath temperature is 60 ℃, and depositing time is 2 hours, and negative electrode moves in the deposition process, stirs plating bath; Metal base is taken out in the deposition back, washing, and its surface obtains the coating of 30um thickness.
The coating of above-mentioned metal substrate surface is bright, corrosive nature is better.Coating detects through X-ray diffractometer and is characterized by nanocrystalline structure.Coating characterizes through transmission electron microscope, and is as shown in Figure 2, is the amorphous nano-crystalline composite structure.
Comparing embodiment 1:
Present embodiment is the comparative example of embodiment 1.Among this comparative example, do not contain reductive agent in the plating bath, gained coating is corronel.Specific as follows.
Electroplate liquid formulation is: solvent is a deionized water, cupric phosphate 8g/L, single nickel salt 20g/L, boric acid 10g/L.
Use the preparation technology of above-mentioned corronel plating bath plating preparation corronel coating following:
(1) metal base is a soft steel; Metal substrate surface is carried out oil removing, oxide film dissolving handle, its detailed process is identical with step (1) among the embodiment 1;
(2) with deionized water cupric phosphate, single nickel salt and boric acid are configured to the electronickelling copper alloy liquid, the wherein wt percentage concentration is: cupric phosphate 8g/L, single nickel salt 20g/L, boric acid 10g/L;
(3) place the electronickelling copper alloy liquid of step (2) preparation to carry out electroplating deposition the metal base after step (1) processing, its condition is: anode is the pure nickel plate, and cathode current density is 20mA/cm
2, it is 5.5 that plating bath uses ammoniacal liquor to regulate pH, and bath temperature is 60 ℃, and depositing time is 2 hours, and negative electrode moves in the deposition process, stirs plating bath; Metal base is taken out in the deposition back, washing, and its surface obtains the coating of 30um thickness.
The coating light of above-mentioned metal substrate surface.Coating detects through X-ray diffractometer and characterizes, and coating is coarse-grain coating.
Comparing embodiment 2:
Present embodiment is another comparative example of embodiment 1.Among this comparative example, do not contain reductive agent in the plating bath, gained coating is nickel coating.Specific as follows.
Electroplate liquid formulation is: solvent is a deionized water, single nickel salt 20g/L, boric acid 10g/L.
Use the preparation technology of above-mentioned corronel plating bath plating preparation nickel coatings following:
(1) metal base is a soft steel; Metal substrate surface is carried out oil removing, oxide film dissolving handle, its detailed process is identical with step (1) among the embodiment 1;
(2) with deionized water single nickel salt and boric acid are configured to the electronickelling copper alloy liquid, the wherein wt percentage concentration is: single nickel salt 20g/L, boric acid 10g/L;
(3) place the electroplate liquid of step (2) preparation to carry out electroplating deposition the metal base after step (1) processing, its condition is: anode is the pure nickel plate, and cathode current density is 20mA/cm
2, it is 5.5 that plating bath uses ammoniacal liquor to regulate pH, and bath temperature is 60 ℃, and depositing time is 2 hours, and negative electrode moves in the deposition process, stirs plating bath; Metal base is taken out in the deposition back, washing, and its surface obtains the coating of 30um thickness.
The coating light of above-mentioned metal substrate surface.The coating surface light.Coating detects through X-ray diffractometer and characterizes, and coating is coarse-grain coating.
Embodiment 2:
In the present embodiment:
Electroless plating-plating uses the corronel liquid formula to be: solvent is deionized water, cupric chloride 2g/L, nickelous chloride 15g/L, dimethylin borine 2g/L, Trisodium Citrate 20g/L.
Use the preparation technology of the collaborative preparation of above-mentioned corronel liquid electroless plating-plating corronel amorphous base composite cladding following:
(1) metal base is a soft steel; Metal substrate surface is carried out oil removing, oxide film dissolving pre-treatment; Detailed process is: at mass percent concentration is to add an amount of sodium lauryl sulphate in 15% the KOH solution; Obtain mixing solutions, the concentration of sodium lauryl sulphate in mixing solutions is 5g/l, and metal base is put into this mixing solutions; Be 60 ℃ at cleaning temperature and cleaned 5 minutes down, adopt chemical rightenning that metal base is carried out surface film oxide then and remove processing;
(2) with deionized water cupric chloride, nickelous chloride, dimethylin borine and Trisodium Citrate are configured to electroless plating-plating and use corronel liquid; The wherein wt percentage concentration is: cupric chloride 2g/L; Nickelous chloride 15g/L, dimethylin borine 2g/L, Trisodium Citrate 20g/L;
(3) place the electroless plating-plating of step (2) preparation to carry out electroless plating with corronel liquid the metal base after step (1) processing and electroplate collaborative deposition, its condition is: anode is the pure nickel plate, and cathode current density is 30mA/cm
2, it is 7 that plating bath uses ammoniacal liquor to regulate pH, and bath temperature is 55 ℃, and depositing time is 1.5 hours, and the deposition process air stirs plating bath; Metal base is taken out in the deposition back, washing, and its surface obtains the coating of 30um thickness.
The coating of above-mentioned metal substrate surface is bright, corrosive nature is better.Coating detects through X-ray diffractometer and is characterized by nanocrystalline structure, and transmission electron microscope is characterized by the amorphous nano-crystalline composite structure.
Embodiment 3:
In the present embodiment:
Electroless plating-plating uses the corronel liquid formula to be: solvent is deionized water, cupric phosphate 6g/L, single nickel salt 25g/L, formaldehyde 1.5g/L, potassium pyrophosphate sodium 12g/L.
Use the preparation technology of the collaborative preparation of above-mentioned corronel liquid electroless plating-plating corronel amorphous base composite cladding following:
(1) metal base is a soft steel; Metal substrate surface is carried out oil removing, oxide film dissolving pre-treatment; Detailed process is: at mass percent concentration is to add an amount of sodium lauryl sulphate in 12% the KOH solution; Obtain mixing solutions, the concentration of sodium lauryl sulphate in mixing solutions is 6g/l, and metal base is put into this mixing solutions; Be 40 ℃ at cleaning temperature and cleaned 10 minutes down, adopt mechanical polishing that metal base is carried out surface film oxide then and remove processing;
(2) with deionized water cupric phosphate, single nickel salt, formaldehyde and potassium pyrophosphate sodium are configured to electroless plating-plating and use corronel liquid, the wherein wt percentage concentration is: cupric phosphate 6g/L, single nickel salt 25g/L, formaldehyde 1.5g/L, potassium pyrophosphate sodium 12g/L;
(3) place the electroless plating-plating of step (2) preparation to carry out electroless plating with corronel liquid the metal base after step (1) processing and electroplate collaborative deposition, its condition is: anode is the pure nickel plate, and cathode current density is 50mA/cm
2, it is 10 that plating bath uses sodium hydroxide to regulate pH, and bath temperature is 70 ℃, and depositing time is 1 hour, and the deposition process air stirs plating bath; Metal base is taken out in the deposition back, washing, and its surface obtains the coating of 30um thickness.
The coating of above-mentioned metal substrate surface is bright, corrosive nature is better.Coating detects through X-ray diffractometer and is characterized by nanocrystalline structure, and transmission electron microscope is characterized by the amorphous nano-crystalline composite structure.
Embodiment 4:
In the present embodiment:
Electroless plating-plating uses the corronel liquid formula to be: solvent is deionized water, copper sulfate 7g/L, nickelous chloride 60g/L, Peng Qinghuana 3g/L, Hydrocerol A 15g/L.
Use the preparation technology of the collaborative preparation of above-mentioned corronel liquid electroless plating-plating corronel amorphous base composite cladding following:
(1) metal base is a soft steel, and metal base is a soft steel; Metal substrate surface is carried out oil removing, oxide film dissolving handle, its detailed process is identical with step (1) among the embodiment 2;
(2) with deionized water copper sulfate, nickelous chloride, Peng Qinghuana and Hydrocerol A are configured to electroless plating-plating and use corronel liquid, the wherein wt percentage concentration is: copper sulfate 7g/L, nickelous chloride 60g/L, Peng Qinghuana 3g/L, Hydrocerol A 15g/L;
(3) place the electroless plating-plating of step (2) preparation to carry out electroless plating with corronel liquid the metal base after step (1) processing and electroplate collaborative deposition, its condition is: anode is the pure nickel plate, and cathode current density is 15mA/cm
2, it is 11 that plating bath uses sodium hydroxide to regulate pH, and bath temperature is 70 ℃, and depositing time is 3 hours, and the deposition process air stirs plating bath; Metal base is taken out in the deposition back, washing, and its surface obtains the coating of 30um thickness.
The coating of above-mentioned metal substrate surface is bright, corrosive nature is better.Coating detects through X-ray diffractometer and is characterized by nanocrystalline structure, and transmission electron microscope is characterized by the amorphous nano-crystalline composite structure.
Resulting coating among above-mentioned each embodiment is carried out hardness test.The hardness test instrument is nano indenter G200, and test environment is a room temperature.The plastic deformation rate is got by its data computation.Obtain result shown in the following table:
| The embodiment numbering | Hardness (GPa) | Plastic deformation rate (%) |
| Embodiment 1 | ?10.69 | ?0.73 |
| Comparing embodiment 1 | ?6.23 | ?0.55 |
| Comparing embodiment 2 | ?5.95 | ?0.47 |
| Embodiment 2 | ?10.99 | ?0.75 |
| Embodiment 3 | ?10.91 | ?0.74 |
| Embodiment 4 | ?10.36 | ?0.75 |
Above-described embodiment specifies technical scheme of the present invention and beneficial effect; Be understood that the above is merely specific embodiment of the present invention; Be not limited to the present invention; The all any modifications in principle scope of the present invention, made and improvement etc. all should be included within protection scope of the present invention.
Claims (9)
1. corronel liquid is used in electroless plating-plating, it is characterized in that: be solvent with the deionized water, wherein comprise the solute of following percent weight in volume concentration:
Described reductive agent is at least a in sodium hypophosphite, amino borane, oxammonium hydrochloride, Peng Qinghuana, formaldehyde, the Hydrazine Hydrate 80;
Described complexing agent is at least a in Hydrocerol A, Trisodium Citrate, boric acid, Sodium Tetraborate, potassium pyrophosphate sodium, the trisodium phosphate.
2. electroless plating according to claim 1-plating is used corronel liquid, it is characterized in that: described mantoquita is at least a in copper sulfate, cupric pyrophosphate, the cupric chloride.
3. electroless plating according to claim 1-plating is used corronel liquid, it is characterized in that: described nickel salt is at least a in single nickel salt, the nickelous chloride.
4. use the preparation technology of the collaborative preparation of the described corronel liquid electroless plating of arbitrary claim-plating corronel amorphous base composite cladding in the claim 1 to 3, it is characterized in that: comprise the steps:
Step 1, metal substrate surface is carried out oil removing, oxide film dissolving handle;
Step 2, mantoquita, nickel salt, complexing agent, reductive agent are prepared electroless plating-electronickelling copper alloy liquid by weight percentage with deionized water;
Step 3, place the electroless plating-electronickelling copper alloy liquid of step 2 preparation to carry out electroless plating the metal base after handling in the step 1 to electroplate collaborative deposition, its condition is: anode is the pure nickel plate, and cathode current density is 15 ~ 60mA/cm
2, it is 4 ~ 12 that plating bath uses basic soln to regulate pH, and bath temperature is 30 ~ 80 ℃, and depositing time is 1 h ~ 2 hours, and negative electrode moves, stirs plating bath, and circulating filtration is accomplished the preparation of metal base amorphous nano-crystalline composite deposite.
5. the preparation technology of the collaborative preparation of electroless plating according to claim 4-plating corronel amorphous base composite cladding, it is characterized in that: described coating deposition rate is 0.2 ~ 1.0um/min.
6. the preparation technology of the collaborative preparation of electroless plating according to claim 4-plating corronel amorphous base composite cladding, it is characterized in that: the pH value of described plating bath is 4 ~ 12, bath temperature is 30 ~ 80 ℃.
7. the preparation technology of the collaborative preparation of electroless plating according to claim 4-plating corronel amorphous base composite cladding, it is characterized in that: in the described step 3, basic soln is ammonia soln or sodium hydroxide solution.
8. the corronel amorphous base composite cladding that obtains according to the described preparation method of arbitrary claim in the claim 4 to 7 is characterized in that: be made up of amorphous particle and nano-crystalline granule, described nano-crystalline granule is evenly distributed in the amorphous particle.
9. corronel amorphous base composite cladding according to claim 8, it is characterized in that: described nano-crystalline granule is of a size of 1 ~ 10nm.
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